EP0168723A2 - Méthode de préparation de glycosides à partir de glycosylfluorides - Google Patents

Méthode de préparation de glycosides à partir de glycosylfluorides Download PDF

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Publication number
EP0168723A2
EP0168723A2 EP85108316A EP85108316A EP0168723A2 EP 0168723 A2 EP0168723 A2 EP 0168723A2 EP 85108316 A EP85108316 A EP 85108316A EP 85108316 A EP85108316 A EP 85108316A EP 0168723 A2 EP0168723 A2 EP 0168723A2
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EP
European Patent Office
Prior art keywords
fluoride
reaction
fluorides
tetrafluoride
mmol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP85108316A
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German (de)
English (en)
Other versions
EP0168723B1 (fr
EP0168723A3 (en
Inventor
Joachim Prof. Dr. Thiem
Hans-Matthias Dr. Deger
Wolfram Dr. Fritsche-Lang
Merten Dr. Schlingmann
Matthias Kreuzer
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Hoechst AG
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Hoechst AG
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Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT85108316T priority Critical patent/ATE50775T1/de
Publication of EP0168723A2 publication Critical patent/EP0168723A2/fr
Publication of EP0168723A3 publication Critical patent/EP0168723A3/de
Application granted granted Critical
Publication of EP0168723B1 publication Critical patent/EP0168723B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical

Definitions

  • glucopyranosyl fluorides can be glycosidated with trimethylsilyl ethers or also with unprotected alcohols if silicon tetrafluoride or trimethylsilyl trifluoromethanesulfonate (TMSOTf) is used as catalysts.
  • TMSOTf trimethylsilyl trifluoromethanesulfonate
  • the reaction medium used here is, on the one hand, acetonitrile, which predominantly leads to the ⁇ -glycosides, and, on the other hand, diethyl ether, which predominantly leads to the a-anomer (S. Hashimoto, M. Hayashi and R. Noyori, Tetrahedron Leiters 25 (1984) 1379-1382) .
  • TMSOTf is cheaper and easier to handle, but less effective than silicon tetrafluoride, which is a highly corrosive and aggressive gas.
  • the work-up is complicated when using both catalysts, especially with TMSOTf, since the formation of trifluoromethanesulfonic acid must be avoided here.
  • fluorides of metals of the 4th and 5th group of the periodic table which have an atomic number of at least 22, are particularly advantageous for this glycosidation reaction in the higher, stable and only slightly oxidizing oxidation states own.
  • metal fluorides which also include transition metal fluorides, for example tin and zirconium tetrafluoride, vanadium and antimony pentafluoride and in particular titanium tetrafluoride are suitable.
  • the oily vanadium and antimony pentafluoride is soluble in the reaction system and thus acts in a homogeneous phase, the other fluorides mentioned are solid and insoluble or only slightly soluble, which greatly facilitates their handling and separation.
  • reaction in heterogeneous phase in particular with titanium tetrafluoride, is therefore preferred.
  • the reaction is generally carried out in a solvent or inert medium customary for reactions of sugars, such as acetonitrile, diethyl ether, methylene chloride and / or nitrobenzene or mixtures thereof with benzene, toluene and the like.
  • a solvent or inert medium customary for reactions of sugars, such as acetonitrile, diethyl ether, methylene chloride and / or nitrobenzene or mixtures thereof with benzene, toluene and the like.
  • temperatures from -40 to +60, preferably from -20 to + 30 ° C are used and the process is carried out at atmospheric pressure, although it is also possible to work at elevated or reduced pressure.
  • the fluorides are used in amounts of 1 to 200, preferably 10 to 120 and in particular up to 100, mol%, based on the glycosyl fluoride.
  • Protected hexopyranosyl fluorides are used as glycosyl fluorides, especially those derived from glucose, galactose and mannose. However, derivatives of these sugars, such as 2-deoxy- or 2-amino-2-deoxy-glucose, galactose and mannose as well as glucuronic, galacturonic and mannuronic acids and their derivatives, in particular the esters, amides and nitriles, can also be used .
  • the protective group which can be used is not only the benzyl protective group used in the known process, but also acyl protective groups according to the invention, preferably the acetyl and the benzoyl group. The choice of the protective group can - depending on the fluoride used according to the invention and any solvent used - have an influence on the ratio of the stereoisomers formed.
  • the aglycones are unblocked or in Form of their silyl ether, for example the triethyl, tripropyl, triisopropyl and tributyl ether, or else mixed ether such as t-butyldimethylsilyl ether, but in particular used as trimethylsilyl ether.
  • the reactivity can vary depending on the nature of the alkyl group.
  • aglycones are straight-chain and branched aliphatic monovalent primary, secondary and tertiary C 1 -C 10 and monovalent cycloaliphatic C 5 -C 7 alcohols, but above all monosaccharides, but also disaccharides, in particular from glucose, galactose and Mannose series, the hydroxy groups of which are not to be glycosidated are blocked by suitable protective groups.
  • suitable protective groups such as benzyl or triphenylmethyl ether or acyl or aryloxy or alkoxycarbonyl groups can be used as protective groups.
  • epoxides in glycone or aglycone
  • Phenolic aglycons and complex steroid alcohols such as 5 ⁇ -cholestan-3ß-ol can also be successfully glycosidated.
  • the process products are known in principle and are suitable as intermediates for a large number of syntheses. They are also suitable as model cuts for the investigation of the interaction of antigens with partial structures of cell membranes and are therefore of interest as immunomodulators (KM Yamada and K. Olden, Nature 275 (1978) 179-184, R. Neumeier, Biol. in our time 13 (1983) 33-38).
  • the anomers were separated by column chromatography (silica gel, methylene chloride / diethyl ether 20: 1 v / v).
  • the anomers were separated by column chromatography (silica gel, methylene chloride).
  • glycosides prepared according to Examples 3A) and 3B) have the following characteristics:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Steroid Compounds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP85108316A 1984-07-14 1985-07-05 Méthode de préparation de glycosides à partir de glycosylfluorides Expired - Lifetime EP0168723B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85108316T ATE50775T1 (de) 1984-07-14 1985-07-05 Verfahren zur herstellung von glykosiden aus glykosylfluoriden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3426074 1984-07-14
DE19843426074 DE3426074A1 (de) 1984-07-14 1984-07-14 Verfahren zur herstellung von glykosiden aus glykosylfluoriden

Publications (3)

Publication Number Publication Date
EP0168723A2 true EP0168723A2 (fr) 1986-01-22
EP0168723A3 EP0168723A3 (en) 1987-10-14
EP0168723B1 EP0168723B1 (fr) 1990-03-07

Family

ID=6240701

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85108316A Expired - Lifetime EP0168723B1 (fr) 1984-07-14 1985-07-05 Méthode de préparation de glycosides à partir de glycosylfluorides

Country Status (8)

Country Link
US (1) US4749785A (fr)
EP (1) EP0168723B1 (fr)
JP (1) JPH0631284B2 (fr)
AT (1) ATE50775T1 (fr)
AU (1) AU4487685A (fr)
CA (1) CA1258852A (fr)
DE (2) DE3426074A1 (fr)
DK (1) DK167120B1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990014350A1 (fr) * 1989-05-18 1990-11-29 Hoechst Aktiengesellschaft Procede de production d'acides 1-fluoroglycuroniques et leurs sels, ces nouveaux acides 1-fluoroglycuroniques et leurs sels
EP0531256A1 (fr) * 1991-09-04 1993-03-10 Ciba-Geigy Ag Méthode pour la préparation des glycosides

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1449535A (zh) * 2000-05-01 2003-10-15 Cfph有限责任公司 对事件结果的实时交互下注
US7341517B2 (en) * 2003-04-10 2008-03-11 Cantor Index, Llc Real-time interactive wagering on event outcomes
US7890396B2 (en) 2005-06-07 2011-02-15 Cfph, Llc Enhanced system and method for managing financial market information
US7801784B2 (en) * 2004-06-07 2010-09-21 Cfph, Llc System and method for managing financial market information
US8562422B2 (en) * 2006-09-28 2013-10-22 Cfph, Llc Products and processes for processing information related to weather and other events

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60156699A (ja) * 1984-01-27 1985-08-16 Sankyo Co Ltd 新規なグリコシル化の方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CARBOHYDRATE RESEARCH, Band 149, 1986, Seiten 347-361, Elsevier Science Publishers B.V., Amsterdam, NL; M. KREUZER et al.: "Aufbau von Oligosacchariden mit Glycosylfluoriden unter Lewiss{ure-Katalyse" *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Band 106, Nr. 15, 25. Juli 1984, Seiten 4189-4192, American Chemical Society; K.C. NICOLAOU et al.: "Practical synthesis of oligosaccharides. Partial synthesis of Avermectin B1a" *
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, Nr. 17, 1984, Seiten 1155-1156; K.C. NICOLAOU et al.: "Reactions of glycosyl fluorides. Synthesis of O-, S-, and N-glycosides" *
TETRAHEDRON LETTERS, Band 25, Nr. 13, 1984, Seiten 1379-1382, Pergamon Press Ltd, GB; S. HASHIMOTO et al.: "Glycosylation using glucopyranosyl fluorides and silicon-based catalysts. Solvent dependency of the stereoselection" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990014350A1 (fr) * 1989-05-18 1990-11-29 Hoechst Aktiengesellschaft Procede de production d'acides 1-fluoroglycuroniques et leurs sels, ces nouveaux acides 1-fluoroglycuroniques et leurs sels
EP0531256A1 (fr) * 1991-09-04 1993-03-10 Ciba-Geigy Ag Méthode pour la préparation des glycosides
US5342929A (en) * 1991-09-04 1994-08-30 Ciba-Geigy Corporation Process for the preparation of glycosides

Also Published As

Publication number Publication date
AU4487685A (en) 1986-01-16
DK167120B1 (da) 1993-08-30
EP0168723B1 (fr) 1990-03-07
DK320685A (da) 1986-01-15
DE3426074A1 (de) 1986-01-23
JPS6136294A (ja) 1986-02-20
DE3576343D1 (de) 1990-04-12
JPH0631284B2 (ja) 1994-04-27
EP0168723A3 (en) 1987-10-14
DK320685D0 (da) 1985-07-12
ATE50775T1 (de) 1990-03-15
CA1258852A (fr) 1989-08-29
US4749785A (en) 1988-06-07

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